WO2011058778A1 - 分離膜ユニット及びこれを備えた分離膜エレメント - Google Patents

分離膜ユニット及びこれを備えた分離膜エレメント Download PDF

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Publication number
WO2011058778A1
WO2011058778A1 PCT/JP2010/060536 JP2010060536W WO2011058778A1 WO 2011058778 A1 WO2011058778 A1 WO 2011058778A1 JP 2010060536 W JP2010060536 W JP 2010060536W WO 2011058778 A1 WO2011058778 A1 WO 2011058778A1
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WIPO (PCT)
Prior art keywords
separation
separation membrane
membranes
membrane unit
active layer
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PCT/JP2010/060536
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English (en)
French (fr)
Japanese (ja)
Inventor
勝視 石井
敦 廣
川口　佳秀
原田　憲章
修 林
敦子 水池
Original Assignee
日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to EP10829738.3A priority Critical patent/EP2500084A4/de
Priority to CN201080050546.8A priority patent/CN102596377B/zh
Priority to US13/509,245 priority patent/US20120228213A1/en
Publication of WO2011058778A1 publication Critical patent/WO2011058778A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/08—Flat membrane modules
    • B01D63/082—Flat membrane modules comprising a stack of flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/14—Pleat-type membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/12—Specific discharge elements

Definitions

  • the present invention relates to a separation membrane unit for producing a permeate by filtering an object to be filtered and a separation membrane element including the separation membrane unit.
  • General filtration methods and cross-flow filtration methods are generally known as methods of filtering raw water (filtered objects) such as drainage and seawater using a reverse osmosis method or the like.
  • the total filtration method is a method of filtering the whole amount of raw water to be supplied.
  • the raw water is supplied in a direction orthogonal to the separation membrane.
  • the cross-flow filtration method clogs the separation membrane by supplying raw water in a direction parallel to the separation membrane and circulating the raw water as necessary while filtering a part of the raw water through the separation membrane. It is a system that can be filtered while suppressing the above.
  • a separation membrane unit having a separation membrane that is folded back into a plurality of pleats is known.
  • a plurality of separation membranes are folded back in a pleat shape and folded to form a channel between adjacent separation membranes (network spacer). Is arranged.
  • a separation active layer (skin layer) is formed on one surface of a sheet-like porous substrate, and raw water is supplied to the separation active layer side to separate the separation active layer and the porous substrate.
  • the permeated water can be obtained by passing the water.
  • the separation membrane unit has an asymmetric structure. In this case, uneven flow tends to occur, and there is a possibility that filtration by the crossflow filtration method cannot be performed satisfactorily.
  • the separation membrane unit according to the present invention is a separation membrane unit for producing a permeate by filtering an object to be filtered, and a separation active layer is formed on one surface of each sheet-like porous substrate.
  • the two separation membranes are overlapped so that the separation active layers face each other, and the two separation membranes are folded back into a plurality of pleats so that one side of the two separation membranes is provided. Folded portions are alternately formed on one side and the other side.
  • the two separation membranes each having the separation active layer formed on one surface of the sheet-like porous substrate are overlapped so that the separation active layers face each other.
  • the separation active layer is not exposed on one side and the other side where the folded portion is formed. Therefore, damage to the isolation active layer can be prevented with a simple configuration.
  • the two separation membranes stacked so that the separation active layers face each other have a symmetric structure, and the two separation membranes also have a symmetric structure even when they are folded back multiple times in a pleat shape. Therefore, compared to the case of an asymmetric structure in which a single separation membrane having a separation active layer formed on one surface is folded back multiple times in a pleat form, drift is less likely to occur, and filtration by the crossflow filtration method is good. Can be done.
  • the separation membrane unit according to the present invention is characterized in that a supply-side flow path as a flow path of the supplied filtration object is formed between the two separation membranes.
  • the filtration object is filtered by the two separation membranes by supplying the filtration object into the supply-side flow path formed between the two separation membranes, A permeate can be generated outside the separation membrane.
  • the separation membrane unit according to the present invention is characterized in that it is provided between the two separation membranes and includes a supply-side channel material for forming the supply-side channel.
  • the supply-side channel can be reliably formed by the supply-side channel material provided between the two separation membranes, so that the filtration object can be filtered well even in the folded portion or the like. can do.
  • the separation membrane unit according to the present invention is characterized in that a permeate flow path as a permeate flow path is formed on one side and the other side of the two separation membranes.
  • a permeate generated by filtering an object to be filtered by two separation membranes is transmitted to one side and the other side of the two separation membranes. It can be efficiently transported through the side channel.
  • two permeation membranes folded so as to have a symmetrical structure are symmetrically arranged on one side and the other side of the separation side flow path, the entire structure becomes symmetrical. Filtration can be performed stably.
  • the separation membrane unit is accommodated in the exterior material having a cylindrical cross section, the inner peripheral surface of the exterior material formed on one side and the other side of the two separation membranes, respectively. Since a permeate-side flow path can be provided in an empty space between the two, a space for installing two separation membranes can be ensured to the maximum, and filtration can be performed more efficiently.
  • the separation active layer preferably contains a polyamide-based resin.
  • the separation membrane element according to the present invention includes the separation membrane unit and an exterior material that covers the outside of the separation membrane unit.
  • FIG. 1 is an exploded cross-sectional view showing an example of a lamination mode of a separation membrane 1 constituting a separation membrane unit according to an embodiment of the present invention.
  • a channel material 2 as a spacer is sandwiched between two separation membranes 1.
  • the separation membrane 1 may be an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, a dialysis membrane, or the like, but in the case of a reverse osmosis membrane or an ultrafiltration membrane from the relationship between the pressure of raw water and the flow rate of permeated water. It is effective for.
  • the two separation membranes 1 have the same configuration, and each includes a sheet-like porous substrate 3 and a separation active layer (skin layer) 4 formed on one surface of the porous substrate 3.
  • the separation membrane 1 may further include not only the porous substrate 3 and the separation active layer 4 but also other layers. These two separation membranes 1 are overlapped on both sides with the flow path material 2 sandwiched so that the separation active layer 4 faces each other. Thus, the two separation membranes 1 and the flow path material 2 are laminated in a state where the separation active layer 4 of each separation membrane 1 is in contact with the surface of the flow path material 2 facing each other.
  • the porous substrate 3 can be formed using, for example, polysulfone, polyethersulfone, PVDF, polyethylene, polyimide, epoxy, or the like. In addition to the above materials, the porous substrate 3 may be reinforced with a reinforcing material such as a nonwoven fabric, a woven fabric, a knitted fabric, or a net. The thickness of the porous substrate 3 is about 20 to 1000 ⁇ m.
  • the separation active layer 4 is formed of a dense and non-porous thin film, and the material of the separation active layer 4 is not particularly limited, and examples thereof include cellulose acetate, ethyl cellulose, polyether, polyester, polyamide, and silicon.
  • the channel material 2 can be formed using, for example, a knitted fabric or a net.
  • the separation active layer 4 containing a polyamide-based resin obtained by polymerizing a polyfunctional amine component and a polyfunctional acid halogen component is preferable.
  • the polyfunctional amine component is a polyfunctional amine having two or more reactive amino groups, and examples thereof include aromatic, aliphatic, and alicyclic polyfunctional amines.
  • aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino.
  • aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino.
  • examples include benzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidole, xylylenediamine and the like.
  • Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, and n-phenyl-ethylenediamine.
  • Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethylpiperazine, and the like.
  • polyfunctional amines may be used alone or in combination of two or more.
  • the polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
  • polyfunctional acid halide examples include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
  • aromatic polyfunctional acid halide examples include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonylbenzene dicarboxylic acid.
  • An acid dichloride etc. are mentioned.
  • Examples of the aliphatic polyfunctional acid halide include propanedicarboxylic acid dichloride, butanedicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propanetricarboxylic acid trichloride, butanetricarboxylic acid trichloride, pentanetricarboxylic acid trichloride, glutaryl halide, adipoid Examples include luhalides.
  • Examples of the alicyclic polyfunctional acid halide include cyclopropanetricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentanetricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, and tetrahydrofuran.
  • Examples thereof include tetracarboxylic acid tetrachloride, cyclopentane dicarboxylic acid dichloride, cyclobutane dicarboxylic acid dichloride, cyclohexane dicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.
  • polyfunctional acid halides may be used alone or in combination of two or more.
  • an aromatic polyfunctional acid halide it is preferable to use an aromatic polyfunctional acid halide.
  • a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, or polyacrylic acid, a polyhydric alcohol such as sorbitol, glycerin, or the like may be copolymerized.
  • the method for forming the separation active layer 4 containing the polyamide-based resin on the surface of the porous substrate 3 is not particularly limited, and any known method can be used. For example, an interfacial condensation method, a phase separation method, a thin film coating method, and the like can be given.
  • the interfacial condensation method comprises forming an isolation active layer 4 by bringing an aqueous amine solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component to cause interfacial polymerization, A method of placing the separation active layer 4 on the porous substrate 3 or a method of directly forming the separation active layer 4 of the polyamide resin on the porous substrate 3 by the interfacial polymerization on the porous substrate 3 It is. Details of the conditions of the interfacial condensation method are described in JP-A-58-24303 and JP-A-1-180208, and those known techniques can be appropriately employed.
  • an aqueous solution coating layer comprising an aqueous amine solution containing a polyfunctional amine component is formed on the porous substrate 3, and then an organic solution containing the polyfunctional acid halide component and the aqueous solution coating layer are brought into contact with each other to form an interface.
  • a method of forming the separation active layer 4 by polymerizing is preferable.
  • the concentration of the polyfunctional amine component in the aqueous amine solution is not particularly limited, but is preferably 0.1 to 5% by weight, more preferably 1 to 4% by weight. If the concentration of the polyfunctional amine component is too low, defects such as pinholes are likely to occur in the separation active layer 4 and the salt blocking performance tends to be reduced. On the other hand, when the concentration of the polyfunctional amine component is too high, the film thickness becomes too thick, the permeation resistance increases, and the permeation flux tends to decrease.
  • the concentration of the polyfunctional acid halide component in the organic solution is not particularly limited, but is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight. If the concentration of the polyfunctional acid halide component is too low, the unreacted polyfunctional amine component tends to remain, or defects such as pinholes are likely to occur in the separation active layer 4 and the salt blocking performance tends to decrease. is there. On the other hand, when the concentration of the polyfunctional acid halide component is too high, the unreacted polyfunctional acid halide component tends to remain, the film thickness becomes too thick, and the permeation resistance increases, and the permeation flux tends to decrease. It is in.
  • the organic solvent used in the organic solution is not particularly limited as long as it has low solubility in water, does not deteriorate the porous substrate 3, and dissolves the polyfunctional acid halide component.
  • cyclohexane, heptane, And saturated hydrocarbons such as octane and nonane, and halogen-substituted hydrocarbons such as 1,1,2-trichlorotrifluoroethane is preferred.
  • a saturated hydrocarbon having a boiling point of 300 ° C. or lower, more preferably a boiling point of 200 ° C. or lower.
  • additives can be added to the amine aqueous solution and the organic solution for the purpose of facilitating film formation and improving the performance of the resulting composite semipermeable membrane.
  • the additive include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and sodium laurylsulfate, sodium hydroxide that removes hydrogen halide generated by polymerization, trisodium phosphate, and triethylamine.
  • surfactants such as sodium dodecylbenzenesulfonate, sodium dodecylsulfate, and sodium laurylsulfate
  • sodium hydroxide that removes hydrogen halide generated by polymerization
  • trisodium phosphate triethylamine.
  • the thickness of the separation active layer 4 formed on the porous substrate 3 is not particularly limited, but is usually about 0.05 to 2 ⁇ m, preferably 0.1 to 1 ⁇ m.
  • the two separation membranes 1 and the flow path material 2 that are superposed on each other as described above are used in a state where a plurality of folds are folded back into a pleat shape (bellows shape). . Therefore, it is preferable that the two separation membranes 1 and the flow path material 2 are both flexible, and it is preferable that the separation membrane 1 and the flow path material 2 are resistant to cracking even if they are bent 180 ° repeatedly.
  • FIG. 2 is a schematic perspective view showing a configuration example of the separation membrane unit 10.
  • the separation membrane unit 10 is for generating permeated water (permeate) by filtering raw water (filtered object), and two separation membranes stacked on each other in the mode shown in FIG. 1 and the flow path material 2 are folded back in a pleated manner as shown in FIG. 2 so that they are alternately folded back to one side and the other side (upper and lower in FIG. 2). Part 5 is formed.
  • each folded portion 5 extends in a direction B perpendicular to the stacking direction A of the separation membrane 1 and the flow path material 2 as described above, and adjacent folded portions 5 are arranged in the stacking direction A.
  • the separation membrane unit 10 employs a cross-flow filtration method in which raw water such as waste water or seawater is supplied along a direction B parallel to the separation membrane 1 and is folded back multiple times in a pleated shape.
  • Raw water is supplied from one end of the two separation membranes 1 and the flow path material 2 on the upstream side in the supply direction B.
  • the supplied raw water passes between the two separation membranes 1 through the raw water flow passage (supply side flow passage) formed between the two separation membranes 1 by the flow passage material 2, and the separation membrane 1.
  • the channel material 2 functions as a supply-side channel material for forming the supply-side channel, and the supply-side channel can be reliably formed by the supply-side channel material.
  • raw water can be filtered well.
  • the flow direction of raw water A water collecting pipe 6 extending in parallel with the supply direction B is provided. These water collecting pipes 6 are provided on one side and the other side where the folded-back portions 5 are formed with respect to the two separation membranes 1 and the flow path material 2 which are folded back in a plurality of pleats.
  • a permeate-side flow path 7 as a flow path of permeated water is formed inside.
  • the permeated water generated by filtering the raw water flowing in the supply direction B between the two separation membranes 1 by the separation membrane 1 is outside the two separation membranes 1, more specifically, the upper side in FIG. And it flows out below and is collected in the water collection pipe
  • the permeated water collected in this way is guided to the outside of the separation membrane unit 10 through the water collection pipe 6.
  • a sealing portion 8 is provided between two separation membranes 1 and a flow path member 2 that are folded back multiple times in a pleat shape, and a water collecting pipe 6 provided on one side and the other side thereof. Is formed.
  • This sealing portion 8 is for separating raw water passing between the two separation membranes 1 and permeated water generated outside the two separation membranes 1, and only the permeated water is sealed. It is guided to the water collecting pipe 6 through the stop 8.
  • the water collecting mechanism may be formed in the sealing portion 8 or may be formed separately from the sealing portion 8.
  • two separation membranes 1 each having a separation active layer 4 formed on one surface of a sheet-like porous substrate 3 are superposed so that the separation active layer 4 faces each other. Therefore, the separation active layer 4 is not exposed on one side and the other side (upper and lower in FIG. 2) where the folded portion 5 is formed. Therefore, damage to the isolation active layer 4 can be prevented with a simple configuration.
  • the two separation membranes 1 superposed so that the separation active layers 4 face each other have a symmetric structure, and the two separation membranes 1 are folded back into a plurality of pleats as shown in FIG. But it becomes a symmetric structure. Therefore, as compared with the case of an asymmetric structure in which a single separation membrane 1 having a separation active layer 4 formed on one surface is folded back into a plurality of pleats, drift is less likely to occur, and filtration by a crossflow filtration method is performed. Can be performed satisfactorily.
  • the permeated water generated by filtering the raw water by the two separation membranes 1 is provided on one side and the other side (upper and lower in FIG. 2) of the two separation membranes 1, respectively. Further, it can be efficiently conveyed through the water collecting pipe 6. In particular, if the water collecting pipes 6 are symmetrically arranged on one side and the other side of the two separation membranes 1 folded so as to have a symmetrical structure, the entire structure becomes symmetrical. Filtration can be performed stably.
  • FIG. 3A to 3C are schematic cross-sectional views showing a mode when the separation membrane 1 is folded back.
  • FIG. 3A is an example showing a state in which the two separation membranes 1 and the channel material 2 that are superposed on each other are in the middle of being folded back into a pleat shape, and a V-shape is formed so that the folded portion 5 has an acute angle. Is bent.
  • FIG. 3B is an example showing a state in which the two separation membranes 1 and the channel material 2 that are superposed on each other are folded back in a pleated manner, but the folded portion 5 is U-shaped. It has a curved shape.
  • the shape of the convex portion various shapes such as a rhombus, a parallelogram, an ellipse, an oval, a circle, a square, and a triangle may be adopted as long as the flow path of raw water can be secured. Can do.
  • the folded portion 5 of the separation membrane 1 is bent in a V shape.
  • the shape is not limited to such a shape.
  • the folded portion 5 may be curved in a U shape. Good.
  • FIG. 3A to FIG. 3C show only one example of the mode when the separation membrane 1 is folded back, and other various shapes can be adopted as long as the two separation membranes 1 are folded back multiple times. Can do.
  • a method of folding the two separation membranes 1 there are, for example, a method of folding the two separation membranes 1 in a state of being overlapped, and a method of folding the separation membranes 1 after being folded.
  • a folded portion 5 having a shape corresponding to the member is formed by pressing a member such as a guillotine blade against the separation membrane 1 and folding the separation membrane 1 at the pressed portion. be able to.
  • a method of folding the separation membrane 1 using a pinch roll or a pinch bar is also conceivable.
  • FIG. 4A to 4C are schematic perspective views showing an example of the configuration of the separation membrane element 100.
  • the separation membrane unit 10 can be used in a state in which the outer side is covered with an exterior material 9 or the like as necessary, or an end member (not shown) is provided at an axial end.
  • a separation membrane element 100 is configured by providing a separation membrane unit 10 in a cylindrical exterior member 9.
  • FIG. 4A shows an example of the separation membrane element 100 in which the separation membrane unit 10 of FIG. Since the two separation membranes 1 and the flow path member 2 that are folded back multiple times in a pleat shape have a rectangular cross section, it is preferable to use the exterior material 9 having an inner diameter slightly larger than the length of the diagonal line.
  • the sealing portions 8 are provided respectively on one side and the other side (upper and lower in FIG. 4A) of the two separation membranes 1 and the flow path material 2 that are folded back in a pleat shape.
  • a space 101 for circulating raw water between these sealing portions 8 is formed, and permeated water is circulated between each sealing portion 8 and the inner peripheral surface of the exterior material 9 facing it.
  • a space 102 is formed.
  • a seal member may be provided.
  • the space 102 is filled with the sealing portion 8 except for the permeate-side flow path 7, and therefore the outer peripheral surface of the sealing portion 8 is the inner peripheral surface of the exterior material 9. It becomes the shape corresponding to.
  • the permeation-side flow path 7 having an arbitrary cross-sectional area can be formed according to the shape of the hole formed in the sealing portion 8. it can.
  • the separation membrane unit 10 when the separation membrane unit 10 is accommodated in the exterior member 9 having a cylindrical cross section, one side and the other side of the two separation membranes 1 are used. Since the permeation-side flow path 7 can be provided in the empty space (space 102) between the inner peripheral surface of the exterior material 9 formed in each of (upper and lower in FIGS. 4A to 4C) The installation space for the separation membrane 1 can be secured to the maximum, and filtration can be performed more efficiently.
  • the exterior material 9 is not limited to a circular cross section, and may be other shapes such as a rectangular shape, or the exterior material 9 can be omitted. Even in the case where the packaging material 9 is omitted, in this embodiment, the two separation films 1 are overlapped so that the separation active layer 4 faces each other, and the separation active layer 4 is not exposed. Therefore, there is no possibility that the separation active layer 4 is damaged.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
PCT/JP2010/060536 2009-11-11 2010-06-22 分離膜ユニット及びこれを備えた分離膜エレメント WO2011058778A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP10829738.3A EP2500084A4 (de) 2009-11-11 2010-06-22 Trennmembraneneinheit und trennmembranenelement damit
CN201080050546.8A CN102596377B (zh) 2009-11-11 2010-06-22 分离膜单元和具备该分离膜单元的分离膜元件
US13/509,245 US20120228213A1 (en) 2009-11-11 2010-06-22 Separation membrane unit and separation membrane element with same

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JP2009-258334 2009-11-11
JP2009258334A JP2011101864A (ja) 2009-11-11 2009-11-11 分離膜ユニット及びこれを備えた分離膜エレメント

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WO (1) WO2011058778A1 (de)

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CN107106988B (zh) * 2014-12-26 2020-09-22 东丽株式会社 分离膜元件
CN107835673B (zh) * 2015-05-08 2021-01-26 Emd密理博公司 薄膜粘合的扁平包装
EP3542891A4 (de) * 2016-11-17 2020-06-17 Nitto Denko Corporation Trennmembran und laminat
CN113272038B (zh) * 2018-12-28 2023-06-06 日东电工株式会社 过滤器褶裥组件和空气过滤器单元
US11439948B2 (en) * 2019-12-09 2022-09-13 Mahle International Gmbh Membrane module for mitigating evaporative fuel emissions of automobiles
CN115196719A (zh) * 2022-03-25 2022-10-18 浙江卫蓝环保科技有限公司 一种板式复合滤芯

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JP2011101864A (ja) 2011-05-26
EP2500084A1 (de) 2012-09-19
CN102596377A (zh) 2012-07-18
EP2500084A4 (de) 2014-07-02
US20120228213A1 (en) 2012-09-13

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